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Energy Conversion and Management: Murat Kılıç, Aysße Eren Pütün, Basßak Burcu Uzun, Ersan Pütün
Energy Conversion and Management: Murat Kılıç, Aysße Eren Pütün, Basßak Burcu Uzun, Ersan Pütün
Department of Chemical Engineering, Faculty of Engineering, Anadolu University, 26480 Eskisehir, Turkey
Department of Material Science and Engineering, Faculty of Engineering, Anadolu University, 26480 Eskisehir, Turkey
a r t i c l e
i n f o
Article history:
Received 1 July 2013
Accepted 3 November 2013
Available online 3 December 2013
Keywords:
Co-pyrolysis
Oil shale
Biomass
Euphorbia rigida
a b s t r a c t
In this study, co-pyrolytic behaviors of oil shale and Euphorbia rigida were investigated at different temperatures in a xed bed reactor at 450, 500, and 550 C with a heating rate of 10 C/min in the presence of
nitrogen atmosphere. The obtained solid product (char) and liquid product (tar) were analyzed by using
different types of characterization techniques. Experimental results showed co-pyrolysis of oil shale and
biomass could be an environmental friendly way for the transformation of these precursors into valuable
products such as chemicals or fuels.
2013 Elsevier Ltd. All rights reserved.
1. Introduction
Although, consumption of fossil fuels causes environmental
problems such as global warming, acidication of earth caused
by acid rains and dispersing of metals originating from fossil fuels
they supply a large quantity of energy which is demanding by the
world. One of the most important reasons for this fact is the rapid
growth in population coupled with industrial and technological
developments and this leads the depletion of limited fossil fuel resources of the world [1]. This view has led the researches to the
alternative and renewable energy sources which should be not
only environment friendly but also sustainable, as it plays an
important role in reducing CO2 emissions and increasing the share
of renewable sources in the energy balance. This also means reducing the growing dependence of imported energy sources of developing countries. Looking at this point renewable energy sources
are expected to be economically competitive with conventional
energy sources in the future [2].
Among the renewable energy sources, biomass is a primary candidate because of being the only renewable source of xed carbon,
which is essential in the production of conventional hydrocarbon
liquid fuels by thermochemical methods mainly pyrolysis [3].
Biomass is a mixture of hemicellulose, cellulose, lignin and minor
amounts of other organics each of which converts to synthetic
fuels at different rates and also by various mechanisms [4]. For
having abundant biomass sources Turkey is an important agricul-
Corresponding author. Tel.: +90 222 321 3550x6518; fax: +90 222 323 9501.
E-mail address: eputun@anadolu.edu.tr (E. Ptn).
0196-8904/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.enconman.2013.11.002
462
hydrocarbons. It can be used directly as a fuel such as marine diesel. It can also be added to petroleum renery feedstocks or upgraded by catalysts to produce good quality rened fuels.
Moreover it has a potential to be used as chemical feedstock. Tars
are the important and preferred products because of their high caloric values, ease of transportation and storage. Low nitrogen and
sulfur contents and convertibility into valuable chemicals are the
other signicant factors. The third product gas having a high caloric value may also be used as a fuel [10].
Another approach in utilization of carbonaceous materials is coprocessing [11]. Co-pyrolysis and co-gasication techniques have
received much attention in recent years for allowing the reduction
of the volume of biomass waste, recovering chemicals and replacing fossil fuels [12]. On the other hand, their conversion to renewable energy would be attractive for solving pollution problems,
reducing greenhouse gases emissions and more over providing
clean fuel with low sulfur content [13]. Primary importance is
the impact on the emissions of CO2, NOx, SOx, and volatile organic
compounds (VOC) and polyaromatic hydrocarbons (PAH) [14].
Consequently, it is desirable to co-utilize the two sources for sustainable utilization of oil shale and also to minimize the impact
on the environment by the use of oil shale [15].
Terpene hydrocarbons are high energy capacity hydrocarbons.
They could be used as an engine fuel and as chemical feedstock.
One of the well-known terpenoid biomass is Euphorbiaceae family
and Euphorbia rigida, a member of Euphorbiaceae, grows on the arid
lands of Middle Anatolia in abundant quantities and without any
requirement of special labor, made this non-edible plant as a
new attractive energy source. About 2000 species have been
reported throughout the world, chiey in tropical regions and it
is known that 80 species of Euphorbia are found in Turkey [16].
E. rigida grows in a very close region to the oil shale reserves. There
are several reported studies for the pyrolysis of oil shale and
E. rigida individually [1623]. But there is not a study conducted
prior to this study including co-pyrolysis of oil shale with E. rigida.
Adding E. rigida to oil shale is expected to affect the yield and
quality of the tar in a good way. Co-pyrolysis of biomass with oil
shale will also decrease the emissions of gaseous carbons when it
is compared to pyrolysis of oil shale alone. On the basis of these
considerations, here in this study co-pyrolysis of oil shale and E.
rigida by slow pyrolysis and characterization of obtained solid
and liquid products was investigated.
2. Experimental
2.1. Materials
Raw E. rigida samples were collected from South-western Anatolia between Afyon and Denizli, Turkey. The plants were harvested between April and June. E. rigida was washed with
distilled water to remove any adhering substance and dried at
room temperature, ground in a high-speed rotary cutting mill
and stored in a cool and dark room. The plants leaves and stalks
were used in experiments. A particle size in the range from 0.425
to 1.25 mm was used for co-pyrolysis experiments. Oil shale samples used in this research were collected from Seyitmer which
were crushed, homogenized and ground in a high-speed rotary
cutting mill and a particle size in the range from 0.425 to
0.60 mm was used for co-pyrolysis experiments.
Proximate and ultimate analyses performed on oil shale and ER
to investigate the characteristics of raw materials. The ASTM Standard Test Method for Proximate Analysis of Wood Fuels (E 870-82)
was used to determine the weight fractions of moisture, volatile,
and ash contents. The xed carbon was obtained by subtracting
the percentages of volatile matter, moisture and ash from 100%.
dW
1 dWt
dt
W 0 dt
463
Table 1
Characteristics (wt.%) of E. rigida, oil shale, and E. rigida-oil shale blend (as received).
E. rigida
Oil shale
3.00
6.40
76.80
13.80
5.78
66.50
19.87
7.85
4.20
38.84
43.34
13.62
49.56
5.16
1.20
44.08
1.24
0.67
16.26
23.40
3.60
0.30
1.10
1.62
0.21
5.87
By difference.
Temperature (C)
Fig. 2. TG vs temperature curve of E. rigida, oil shale, and E. rigida-oil shale blend.
464
dx
E
1 x
A exp
dt
RT
ln(-ln(1-x)/T2)
(a)
Reaction 1
Reaction 3
Reaction 2
where A is pre-exponential factor, E is activation energy, T is temperature, t is time, x is weight loss fraction or pyrolysis conversion
which can be calculated by
W0 Wt
W0 Wf
ln1 x
T2
ln
AR
2RT
E
1
HE
E
RT
Reaction 1
ln(-ln(1-x)/T2)
ln
(b)
Reaction 2
Since it may be shown that for most values of E and for the temperature range of the pyrolysis, the expression ln[AR/HE(1 2RT/
E)] in Eq. (4) is essentially constant, if the left side of Eq. (4) is plotted versus 1/T, a straight line may be obtained if the process can be
assumed as a rst order reaction. From the slope, E/R, the activation energy E can be determined, and by taking the temperature at
which Wt = (W0 + Wf) /2 in the place of T in the intercept term of Eq.
(4), the pre-exponential factor A can also be determined. Due to the
release of some volatiles by physical processes before a signicant
weight loss rate takes place, differences in the baseline of some
proles were found that make it difcult to determine Ti. To solve
this difculty, the beginning temperature of pyrolysis Ti is dened
as temperature at x = 5%. Similar problems are found for the calculation of TF in some proles. Consequently, TF is calculated at
x = 95% similar to Ti [26,29].
Fig. 3 shows the typical plots of ln[ln(1 x)/T2] versus 1/T,
indicating that E. rigida pyrolysis process have three independent
rst order reactions whereas oil shale pyrolysis process have two
independent rst order reactions. It can be seen clearly form
Fig. 3 that three and two independent rst order reactions should
be used to describe the E. rigida and oil shale pyrolysis processes,
respectively. Moreover, addition of biomass to oil shale yielded
three independent rst order reactions as E. rigida pyrolysis. Therefore, Eq. (2) is applied separately to each of the stages. To do so, the
1/T (K-1)
Fig. 3. Plot of ln(ln(1 x)/T2) vs 1/T of E. rigida, oil shale, and E. rigida-oil shale
blend.
1/T (K-1)
(c)
ln(-ln(1-x)/T2)
1/T (K-1)
Reaction 1
Reaction 3
Reaction 2
1/T (K-1)
Fig. 4. Plots of ln(ln(1 x)/T2) vs 1/T of (a) E. rigida, (b) oil shale, and (c) E. rigidaoil shale blend pyrolysis calculated by one-step integral method.
conversion x was recalculated for each reaction. The results are given in Fig. 4. From the slope of each line, the value of E and A can be
obtained for different stages.
Table 2 shows the calculated value of activation energy and preexponential factor of the E. rigida, oil shale, and their blends. For
E. rigida, three rst order reactions were used to describe the pyrolysis process (Fig. 4), with the activation energy of 84.3 kJ/mol for
the rst stage, 80.6 kJ/mol for the second one, and 74.6 kJ/mol for
the third one, respectively. For oil shale, two rst order reactions
were used to describe the pyrolysis process (Fig. 4), with the
activation energy of 37.6 kJ/mol for the rst stage and 85.8 kJ/
mol for the second one, respectively. The high correlation coefcient indicates that the corresponding independent rst-order
reaction model ts the experimental data very well. Reaction with
high activation energy needs a high temperature or a long reaction
time. For biomass or oil shale, high activation energy means that
the reaction needs more energy from the surroundings. The change
of activation energy shows E. rigida and oil shale have different
pyrolysis reactivities at different temperatures. In co-pyrolysis,
both activation energies and frequency factors of reactions
465
T (C)
R2
A (dk1)
E (kJ/mol)
E. rigida
134194
194335
335503
711
1153
5369
84.3
80.6
74.6
3.24 10
9.88 106
7.26 104
0.9950
0.9903
0.9600
Oil shale
120295
295505
49
954
37.6
85.8
9.81 102
4.02 105
0.9757
0.9930
Blend
124204
204394
394504
912
1230
3062
50.4
57.8
108.9
7.09 104
8.34 104
1.46 105
0.9918
0.9522
0.9486
Fig. 5. Pyrolysis yields of (a) E. rigida, (b) oil shale, and (c) E. rigida-oil shale blend tar.
Table 3 shows FT-IR spectra results for obtained liquid and solid
products. The OAH stretching vibrations between 3200 and
3600 cm1 indicate the presence of phenols and alcohols. The presence of alkanes is indicated by the absorbance peak of CAH vibrations between 3000 and 2800 cm1 and by 14901325 bands due
to the CAH bending. The absorbance peak between 1775 and
1650 cm1 shows the C@O stretching vibration indicating the presence of aldehydes, ketones and carboxylic acids. The absorbance
peaks between 1680 and 1575 cm1 indicate the presence of alkanes and nitrogenated compounds. The peaks between 1300
and 950 cm1 are due to the presence of primary, secondary and
tertiary alcohols and phenols are showing the CAO stretching
and OAH bending. The presence of single, polycyclic and substituted aromatic groups can be seen from the absorbance peaks between 900 and 650 cm1.
GC/MS analyses were carried out with the pyrolysis tars obtained at optimum temperature. The objective was to get an idea
of the nature and type of compounds of such oils, in order to establish the possible ways of reusing or treating them. Fig. 6 shows the
GC/MS chromatogram of tars. The compounds identied in the tars
Table 3
Functional group composition.
Wave number (cm1)
Functional groups
Compound class
E. rigida
Oil shale
Blend 1:1
36003200
31003010
30002800
17751650
16801575
14901325
1300950
AOH stretching
CAH stretching
CAH stretching
C@O stretching
C@C stretching
CAH bending
CAO stretching
+/+
/
+/+
/+
/+
+/
+/+
+/+
/+
/+
/+
/+
/+
+/+
+/+
/
/+
/+
/+
/+
+/+
Char/tar.
466
4. Conclusions
Fig. 6. GCMS chromatograms of (a) oil shale, (b) E. rigida, and (c) E. rigida-oil shale
blend tar.
Fig. 7. SEM images of (a) raw E. rigida, (b) E. rigida char, (c) raw oil shale, and (d) oil shale char.
467
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